The　imbalance　between　electrophilic　and　nucleophilic　components　within　Mott–Schottky　(M-S)　electrocatalysts　hinders　oxygen　reduction/evolution　reactions　(ORR/OER).　We　developed　an　innovative　Co/Co3O4-NCF　M-S　catalyst　guided　by　density　functional　theory　(DFT).　By　precisely　screening　nucleophilic　and　electrophilic　components,　Co/Co3O4-NCF　displays　efficient　catalysis　activity　of　ORR　(E1/2　=　0.85　V)　and　OER　(η10　=　320　mV).　Experiments　and　DFT　analyses　revealed　that　strong　interfacial　interactions　in　Co/Co3O4-NCF　cause　harmonized　integration　of　nucleophilic　Co　and　electrophilic　Co3O4　dual　sites,　which　optimizes　antibonding　state　occupancy　of　Co　sites.　Nucleophilic　Co　sites　facilitate　*OH　intermediate　desorption　during　ORR,　while　electrophilic　Co3O4　sites　accelerate　*OOH　intermediate　dissociation　in　OER,　achieving　exceptional　ORR/OER　activity.　Furthermore,　Co/Co3O4-NCF　demonstrates　satisfactory　cell　performances　as　cathodes　for　flexible　Zn–air　batteries　(FZABs)　even　under　extreme　conditions　(−18　to　60　°C),　promoting　the　application　of　FZABs.　This　work　provides　new　insight　into　designing　efficient　M-S　catalysts　by　integrating　balanced　electrophilic　and　nucleophilic　sites.　©　2025　Elsevier　Ltd